Quantifying chemical weathering rates along a precipitation gradient on Basse-Terre Island, French Guadeloupe: new insight from U-series isotopes in weathering rinds

Abstract

Inside soil and saprolite, rock fragments can form weathering clasts (alteration rinds surrounding an unweathered core) and these weathering rinds provide an excellent field system for investigating the initiation of weathering and long term weathering rates. Recently, uranium-series (U-series) disequilibria have shown great potential for determining rind formation rates and quantifying factors controlling weathering advance rates in weathering rinds. To further investigate whether the U-series isotope technique can document differences in long term weathering rates as a function of precipitation, we conducted a new weathering rind study on tropical volcanic Basse-Terre Island in the Lesser Antilles Archipelago. In this study, for the first time we characterized weathering reactions and quantified weathering advance rates in multiple weathering rinds across a steep precipitation gradient. Electron microprobe (EMP) point measurements, bulk major element contents, and U-series isotope compositions were determined in two weathering clasts from the Deshaies watershed with mean annual precipitation (MAP) = 1800 mm and temperature (MAT) = 23 °C. On these clasts, five core-rind transects were measured for locations with different curvature (high, medium, and low) of the rind-core boundary. Results reveal that during rind formation the fraction of elemental loss decreases in the order: Ca ≈ Na > K ≈ Mg > Si ≈ Al > Zr ≈ Ti ≈ Fe. Such observations are consistent with the sequence of reactions after the initiation of weathering: specifically, glass matrix and primary minerals (plagioclase, pyroxene) weather to produce Fe oxyhydroxides, gibbsite and minor kaolinite. Uranium shows addition profiles in the rind due to the infiltration of U-containing soil pore water into the rind as dissolved U phases. U is then incorporated into the rind as Fe-Al oxides precipitate. Such processes lead to significant U-series isotope disequilibria in the rinds. This is the first time that multiple weathering clasts from the same watershed were analyzed for U-series isotope disequlibrian and show consistent results. The U-series disequilibria allowed for the determination of rind formation ages and weathering advance rates with a U-series mass balance model. The weathering advance rates generally decreased with decreasing curvature: ∼0.17 ± 0.10 mm/kyr for high curvature, ∼0.12 ± 0.05 mm/kyr for medium curvature, and ∼0.11 ± 0.04, 0.08 ± 0.03, 0.06 ± 0.03 mm/kyr for low curvature locations. The observed positive correlation between the curvature and the weathering rates is well supported by predictions of weathering models, i.e., that the curvature of the rind-core boundary controls the porosity creation and weathering advance rates at the clast scale. At the watershed scale, the new weathering advance rates derived on the low curvature transects for the relatively dry Deshaies watershed (average rate of 0.08 mm/kyr; MAP = 1800 mm and MAT = 23 °C) are ∼60% slower than the rind formation rates previously determined in the much wetter Bras David watershed (∼0.18 mm/kyr, low curvature transect; MAP = 3400 mm and MAT = 23 °C) also on Basse-Terre Island. Thus, a doubling of MAP roughly correlates with a doubling of weathering advance rate. The new rind study highlights the effect of precipitation on weathering rates over a time scale of ∼100 kyr. Weathering rinds are thus a suitable system for investigating long-term chemical weathering across environmental gradients, complementing short-term riverine solute fluxes.